Two-component developer

ABSTRACT

A two-component developer comprising a toner onto which a hydrophobic silica having an average particle size of 25 nm or more is externally added, and a carrier having a saturation magnetization of from 50 to 95 Am 2 /kg, wherein the carrier has a ratio of surface resistivity to volume resistivity of from 1×10 2  to 1×10 4  m −1  at an electric field strength of 100 V/cm; and a method for development comprising applying the above two-component developer to an electrophotographic device comprising a photoconductor having a peripheral speed of 400 mm/sec or more, and developing a latent image. The two-component developer can be used for the development of a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method or the like.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a two-component developer usedfor the development of a latent image formed in electrophotography,electrostatic recording method, electrostatic printing method or thelike.

[0003] 2. Discussion of the Related Art

[0004] During durablity printing in a high-speed machine or durabilityprinting in a low toner-consumptive mode, such as a long-term printingof fixed images in a low printing ratio, fixed images are likely to bedeteriorated due to a decrease in image density and the like with theembedment of silica. Therefore, there has been proposed to use a tonerin which an external additive having a large particle size is used(Japanese Patent Laid-Open No. Hei 6-332253), or to use a carrier havinga low saturation magnetization. However, the decrease in image density,the background fogging, the toner scattering, the carrier sticking onphotoconductor and the like may be caused.

[0005] An object of the present invention is to provide a two-componentdeveloper which can continuously give high-quality images, even in ahigh-speed machine, without causing the embedment of silica and thecarrier sticking on photoconductor.

SUMMARY OF THE INVENTION

[0006] The present invention relates to a two-component developercomprising:

[0007] a toner onto which a hydrophobic silica having an averageparticle size of 25 nm or more is externally added, and

[0008] a carrier having a saturation magnetization of from 50 to 95Am²/kg, wherein the carrier has a ratio of surface resistivity to volumeresistivity of from 1×10² to 1×10⁴ m⁻¹ at an electric field strength of100 V/cm.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009]FIG. 1 is a cross-sectional view of a device used for thedetermination of the surface resistivity and the volume resistivity ofthe carrier.

DETAILED DESCRIPTION OF THE INVENTION

[0010] One of the greatest features of the present invention resides inthat the ratio of the surface resistivity (Rs) to the volume resistivity(Rv) of a carrier is adjusted. The embedment of silica can be suppressedby increasing the particle size of a silica and lowering the saturationmagnetization of a carrier. However, when the saturation magnetizationof a carrier is low, the formation of the magnetic brush isinsufficient, so that the carrier sticking on a photoconductor is likelyto be caused.

[0011] In the present invention, it has been found that the embedment ofsilica can be prevented and the carrier sticking on photoconductor canbe suppressed by adjusting the ratio of surface resistivity to volumeresistivity (Rs/Rv) of a carrier, so that high-quality images can becontinuously obtained. When the Rs/Rv is outside a specified ratiorange, a problem of low-image density is likely to arise in the high-Rvregion, and the carrier sticking on photoconductor and the backgroundfogging are likely to be caused in the low-Rv region. From theseviewpoints, the ratio of surface resistivity to volume resistivity(surface resistivity/volume resistivity) is from 1×10² to 1×10⁴ m⁻¹,preferably from 2.5×10² to 5×10³ m⁻¹, more preferably from 5×10² to5×10³ m⁻¹ at an electric field strength of 100 V/cm. Here, the surfaceresistivity and the volume resistivity can be determined by the methoddescribed in “TR87-1 Denki Anzen Shishin (Guideline for ElectricalSafety)” (published by the head office of Industrial Safety Association,the Ministry of Labor, 1988).

[0012] Rs is preferably from 1×10¹⁰ to 1×10¹⁷ Ω, more preferably from5×10¹¹ to 1×10¹⁶ Ω, especially preferably from 1×10¹⁴ to 5×10¹⁵ Ω. Also,Rv is preferably from 1×10⁸ to 1×10¹⁶ Ωm, more preferably from 1×10¹⁰ to1×10¹⁴ Ωm, especially preferably from 1×10¹¹ to 5×10¹³ Ωm.

[0013] The carrier has a saturation magnetization of from 50 to 95Am²/kg (emu/g), preferably from 50 to 85 Am²/kg, more preferably from 55to 70 Am²/kg, in order to suppress the impact on the silica by themagnetic brush, thereby preventing the embedment of the silica.

[0014] In the present invention, the carrier comprises a core materialand, if necessary, a coating agent. The core material includesmagnetite, zinc-based ferrite, nickel-based ferrite, copper-basedferrite, copper-zinc-based ferrite, nickel-zinc-based ferrite,manganese-based ferrite, magnesium-based ferrite,manganese-magnesium-based ferrite, manganese-magnesium-strontium-basedferrite, copper-magnesium-based ferrite, manganese-zinc-based ferrite,manganese-copper-zinc-based ferrite, and the like. Among them,manganese-based ferrite, magnesium-based ferrite,manganese-magnesium-based ferrite, andmanganese-magnesium-strontium-based ferrite, each not containing a heavymetal are preferable, from the viewpoints of the environmentalpollutions.

[0015] The surface of the core material may be coated with a knowncoating agent such as a fluororesin, a silicone resin, an acrylic resin,a polyester resin, a polyolefin resin, a polyvinyl resin, apolyvinylidene resin, a phenolic resin, an amino resin, an epoxy resinor a urethane resin. Among them, the silicone resin is preferable fromthe viewpoints of the triboelectric chargeability and the resistanceadjustment.

[0016] The core material can be coated with the resin by, for instance,dissolving the resin in an organic solvent or the like, applying theresulting solution to a carrier surface by immersion, spraying or thelike, thereafter drying, thermally curing or the like, to form a coatingfilm.

[0017] The carrier has a weight-average particle size of preferably from30 to 80 μm, more preferably from 50 to 75 μm, in order to suppress theimpact on the toner, thereby preventing the embedment of the silica.

[0018] In addition, the content of the carrier particles having aparticle size of 22 μm or less is preferably 2% by weight or less, morepreferably 1.5% by weight or less, especially preferably 0.5% by weightor less, from the viewpoint of the fluidity of the carrier.

[0019] In the present invention, any toner comprising a resin binder, acolorant and the like can be used without particular limitation, as longas a specified hydrophobic silica is externally added thereonto.

[0020] The method of hydrophobic treatment of the silica is notparticularly limited. The agent for hydrophobic treatment includeshexamethyldisilazane, dimethyldichlorosilane, silicone oil,methyltriethoxysilane, and the like. Among them, hexamethyldisilazane ispreferable. It is preferable that the amount of the agent forhydrophobic treatment is from 1 to 7 mg/m² per surface area of the fineinorganic particles.

[0021] The hydrophobic silica has an average particle size of 25 nm ormore, preferably from 25 to 1000 nm, more preferably from 30 to 100 nm,in order to prevent the embedment of the silica into the inner portionof the toner.

[0022] The amount of the hydrophobic silica having an average particlesize of 25 nm or more which is externally added is preferably from 0.01to 10 parts by weight, more preferably from 0.1 to 5 parts by weight,especially preferably from 0.5 to 3 parts by weight, based on 100 partsby weight of the untreated toner.

[0023] Incidentally, in the present invention, a hydrophobic silicahaving an average particle size of less than 25 nm, preferably from 5 to20 nm, more preferably from 10 to 20 nm, may also be externally addedtogether therewith.

[0024] The weight ratio of the hydrophobic silica having an averageparticle size of 25 nm or more to the hydrophobic having an averageparticle size of less than 25 mn (hydrophobic silica of 25 nm ormore/hydrophobic silica of less than 25 nm) is preferably from 5/95 to95/5, more preferably from 20/80 to 80/20.

[0025] The resin binder for the toner includes polyesters,styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, andthe like. Among them, the polyesters are preferable. The content of thepolyester is preferably from 50 to 100% by weight, more preferably from90 to 100% by weight, especially preferably 100% by weight, of the resinbinder.

[0026] The raw material monomers for the polyester in the presentinvention are not particularly limited, and known alcohol components andknown carboxylic acid components such as carboxylic acids, carboxylicacid anhydrides, and esters of carboxylic acids are used.

[0027] The alcohol component includes alkylene(2 to 3 carbon atoms)oxide(average number of moles: 1 to 16) adduct of bisphenol A such aspolyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane andpolyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, ethylene glycol,propylene glycol, glycerol, pentaerythritol, trimethylolpropane,hydrogenated bisphenol A, sorbitol, or alkylene(2 to 4 carbon atoms)oxide(average number of moles: 1 to 16) adducts thereof, and the like.These can be used alone or in admixture of two or more kinds.

[0028] In addition, the carboxylic acid component includes dicarboxylicacids such as phthalic acid, isophthalic acid, terephthalic acid,fumaric acid, and maleic acid; a substituted succinic acid of whichsubstituent is an alkyl group having 1 to 20 carbon atoms or an alkenylgroup having 2 to 20 carbon atoms, such as dodecenylsuccinic acid andoctylsuccinic acid; 1,2,4-benzenetricarboxylic acid (trimellitic acid)and pyromellitic acid; acid anhydrides thereof; alkyl(1 to 8 carbonatoms) esters thereof; and the like. These can be used alone or inadmixture of two or more kinds.

[0029] The polyester can be prepared by, for instance, polycondensationof an alcoholic component with a carboxylic acid component at atemperature of 180° to 250° C. in an inert gas atmosphere in thepresence of an esterification catalyst as desired.

[0030] It is preferable that the polyester has an acid value of from 1to 30 mg KOH/g, more preferably from 5 to 20 mg KOH/g, a hydroxyl valueof from 5 to 40 mg KOH/g, a softening point of 100° to 160° C. and aglass transition point of 50° to 70° C.

[0031] As the colorants, all of the dyes and pigments which are used ascolorants for toners can be used, and the colorant includes carbonblacks, Phthalocyanine Blue, Permanent Brown FG, Brilliant Fast Scarlet,Pigment Green B, Rhodamine-B Base, Solvent Red 49, Solvent Red 146,Solvent Blue 35, quinacridone, carmine 6B, disazoyellow, and the like.These can be used alone or in admixture of two or more kinds. In thepresent invention, the toner may be any of black toners, color tonersand full-color toners. The content of the colorant is preferably from 1to 40 parts by weight, more preferably from 3 to 10 parts by weight,based on 100 parts by weight of the resin binder.

[0032] The toner in the present invention may contain a magneticmaterial such as powders of an alloy such as magnetite, hematite orferrite; and powders of a ferromagnetic metal such as iron, cobalt andnickel, in an amount of from 0.5 to 10 parts by weight based on 100parts by weight of the resin binder, in order to prevent tonerscattering.

[0033] Further, the toner may appropriately contain an additive such asa charge control agent, a releasing agent, an electric conductivitymodifier, an extender, a reinforcing filler such as a fibrous substance,an antioxidant, an anti-aging agent, a fluidity improver, and acleanability improver.

[0034] The toner in the present invention can be prepared by a surfacetreatment step comprising mixing an untreated toner with a hydrophobicsilica used as an external additive using a Henschel mixer or the like.The untreated toner is preferably a pulverized toner, and is obtainedby, for instance, homogeneously mixing a resin binder, a colorant andthe like in a mixer such as a Henschel mixer or a ball-mill, thereaftermelt-kneading with a closed kneader, a single-screw or twin-screwextruder, or the like, cooling, roughly pulverizing the resultingproduct using a hammer-mill, and further finely pulverizing with a finepulverizer utilizing a jet stream or a mechanical pulverizer, andclassifying the pulverized product to a given particle size with aclassifier utilizing rotary stream or a classifier utilizing Coandaeffect.

[0035] The toner in the present invention has a volume-average particlesize of preferably from 6 to 12 μm, more preferably from 7 to 9 μm.

[0036] In addition, in order to prevent the lowering of the fluidity ofthe toner by free silica, and to prevent the embedment of the silica,the content of toner particles having a particle size of 5 μm or lesswhich cause an increase in the surface area is preferably from 10 to50%, more preferably from 15 to 45%, on a number basis of the tonerparticles. In addition, the content of the toner particles, ascalculated on a volume basis, is preferably from 0.1 to 15% by volume,more preferably from 0.5 to 9% by volume.

[0037] In the two-component developer of the present invention obtainedby mixing a toner and a carrier, the weight ratio of the toner to thecarrier (toner/carrier) is preferably from 0.5/100 to 8/100, morepreferably from 1/100 to 6/100.

[0038] The two-component developer of the present invention is highlyeffective for the prevention of the carrier sticking on photoconductor,so that the embedment of silica can be prevented without causing thecarrier sticking on photoconductor even when the two-component developeris used for an electrophotographic apparatus such as a copy machine orprinter, comprising a photoconductor having a peripheral speed ofpreferably 400 mm/sec or more, more preferably from 400 to 2000 mm/sec.

EXAMPLES

[0039] [Acid Value and Hydroxyl Value]

[0040] The acid value and the hydroxyl value are measured by a methodaccording to JIS K 0070.

[0041] [Softening Point]

[0042] The softening point refers to a temperature at which a half ofthe resin flows out, when measured by using a flow tester of the “koka”type “CFT-500D” (commercially available from Shimadzu Corporation)(sample: 1 g, rate of raising temperature: 6° C./min, load: 1.96 MPa,and nozzle: φ1 mm×1 mm).

[0043] [Glass Transition Point]

[0044] The glass transition point is determined using a differentialscanning calorimeter “DSC 210” (commercially available from SeikoInstruments, Inc.) with raising the temperature at a rate of 10° C./min.

[0045] [Particle Size Distribution and Average Particle Size of Toner]

[0046] Measuring Apparatus: Coulter Multisizer II (commerciallyavailable from Beckman Coulter)

[0047] Aperture Diameter: 100 μm

[0048] Analyzing Software: Coulter Multisizer AccuComp Ver. 1.19(commercially available from Beckman Coulter)

[0049] Electrolyte: Isotone II (commercially available from BeckmanCoulter)

[0050] Dispersion: 5% electrolyte of EMULGEN 109P (commerciallyavailable from Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6)

[0051] Dispersing Conditions: Ten milligrams of a test sample is addedto 5 ml of a dispersion, and the resulting mixture is dispersed in anultrasonic disperser for 1 minute. Thereafter, 25 ml of an electrolyteis added to the dispersion, and the resulting mixture is dispersed in anultrasonic dispersing apparatus for another 1 minute.

[0052] Measurement Conditions: One-hundred milliliters of an electrolyteand a dispersion are added to a beaker, and the particle sizes of theparticles are determined for 20 seconds under the conditions forconcentration satisfying that the determination for 30000 particles arecompleted in 20 seconds, to obtain its particle size distribution.

[0053] [Surface Resistivity and Volume Resistivity of Carrier]

[0054] Using a device, of which cross-sectional view is shown in FIG. 1,comprising a cell 1 (thickness: 10 mm), an electrode A 2 (diameter: 80mm), an electrode B 3 and an electrode C 4 (weight: 805 g, diameter: 120mm), the cell 1 is filled with 500 g of a carrier so that the carrierhas a thickness of 10 mm when evenly leveled, and the determination iscarried out. The environmental conditions for determination are atemperature of 23° C. and humidity of 45%.

[0055] (1) Surface Resistivity

[0056] The surface resistivity is obtained using an electrodecoefficient of 53.41 from the value of the electric current determinedby using an electrode A 2 as a main electrode, an electrode B 3 as anelectrode couple and an electrode C 4 as a guard electrode, connectingthem to an electrometer “R 8340 A” (commercially available fromAdvantest Corporation), and applying a voltage of 100 V for 60 seconds.

[0057] (2) Volume Resistivity

[0058] The volume resistivity is determined in the same manner as in thesurface resistivity using an electrode A 2 as a main electrode, anelectrode B 3 as a guard electrode and an electrode C 4 as an electrodecouple. Here, the electrode coefficient is 0.503.

[0059] Resin Preparation Example

[0060] The raw materials as shown in Table 1 were reacted in thepresence of a catalytic amount of dibutyltin oxide under nitrogen gasstream, with stirring the ingredients at 200° C. for a resin A or at230° C. for resins B and C. The reaction was allowed to proceed usingthe softening point as determined by the ring and ball method as an endpoint, to give the resins A to C. The softening point (Tm) and the glasstransition point (Tg) of each of the resins are shown in Table 1. TABLE1 Resin A Resin B Resin C BPA-PO ¹⁾ 100 70 70 BPA-EO ²⁾ 30 30 FumaricAcid 100 Succinic Acid 30 10 Dimethyl Terephthalate 45 70 TrimelliticAnhydride 25 20 Tm (° C.) 100 142 118 Tg (° C.) 60 65 73

[0061] Preparation Example 1 of Toner

[0062] Seventy parts by weight of the resin A, 30 parts by weight of theresin B, 6 parts by weight of a colorant “MOGUL L” (commerciallyavailable from Cabot Corporation), 1 part by weight of a charge controlagent “BONTRON S-34” (commercially available from Orient Chemical Co.,Ltd.), 1 part by weight of a releasing agent “Viscol 550P” (commerciallyavailable from SANYO CHEMICAL INDUSTRIES, LTD.) and 1 part by weight ofa magnetite “EPT 1002” (commercially available from Toda Kogyo Corp.)were melt-kneaded at 100° C. using an extruder. The resulting productwas finely pulverized with a jet mill and classified by airclassification, to give an untreated toner having a particle sizedistribution as shown in Table 2.

[0063] To 100 parts by weight of the resulting untreated toner, ahydrophobic silica as shown in Table 2 was mixed and adhered with aHenschel Mixer, to give each of Toners 1 to 6 and Comparative Toners 1to 4.

[0064] Preparation Example 2 of Toner

[0065] The same procedures were carried out as in Preparation Example 1of Toner except that the amount of the resin A used was changed to 50parts by weight and the resin C was used in an amount of 50 parts byweight, to give an untreated toner having a particle size distributionas shown in Table 2. Further, a hydrophobic silica as shown in Table 2was mixed and adhered to the untreated toner, to give Toner 7. TABLE 2Toner Toner Particles Particles Volume- of 5 μm of 5 μm Average or less% or less Particle on Number (% on Volume Hydrophobic Size (μm) Basis)Basis) Silica * Toner 1 7.5 41.3 8.5 NAX50/1 R972/0.9 Toner 2 7.4 33.98.5 NAX50/1.8 Toner 3 7.6 32.0 2.9 RY50/1 R972/0.9 Toner 4 8.6 21.7 2.5NAX50/1 R972/0.9 Toner 5 9.7 16.6 1.3 NAX50/1.8 Toner 6 11.6 13.9 0.6RY50/1.8 Toner 7 8.5 18.2 2.1 NAX50/1.8 Comp. 6.9 24.3 7.0 R972/0.9Toner 1 Comp. 7.1 18.3 4.4 TS530/0.6 Toner 2 Comp. 7.1 18.3 4.4 R972/3Toner 3 Comp. 7.1 18.3 4.4 TS530/3 Toner 4

[0066] Preparation Example of Carrier

[0067] A mixture comprising 40% by mol of manganese oxide (MnO), 15% bymol of magnesium oxide (MgO), 44.5% by mol of iron (III) oxide (Fe₂O₃)and 0.5% by mol of strontium carbonate (SrCO₃) was pulverized and mixedwith a wet-type ball-mill, dried, and thereafter calcined. The resultingproduct was pulverized with a wet-type ball-mill, to a particle size of3 μm or less. A dispersant and a binder were added to this slurry, andthe resulting mixture was granulated and dried with a spray-drier. Theresulting product was backed in an electric oven, and during this timethe sintering temperature was changed to adjust the saturationmagnetization and the grain diameter. Thereafter, the resulting productwas disintegrated, and further classified, to give a core material of aferrite particle. A silicone resin “SR2411” (commercially available fromDow Corning Toray Silicone) was dissolved in a toluene solvent, andcoated onto the above core material using a fluidized bed. The resultingproduct was further sintered, and during this time the resistance of thecarrier was adjusted by changing the amount of “SR2411” and thesintering temperature, to give carriers 1 and 2 as shown in Table 3.

[0068] Similarly, a magnetite, a Cu—Zn-based ferrite, an Mg-basedferrite or an Mn-based ferrite was used as a core material, and theamount of coated resin and the sintering temperature during the coatingwere adjusted, to give Carriers 3 to 5 and Comparative Carriers 1 to 5as shown in Table 3. TABLE 3 Weight- Average Particles of SaturationParticle 22 μm or less Magnetization Rs Rv Rs/Rv Core Material Size (μm)(% by weight) (Am²/kg) (Ω) (Ωm) (m⁻¹) Carrier 1 Mn-Mg-Sr-Based Ferrite62 0 61 1.90 × 10¹⁵ 6.30 × 10¹¹ 3.02 × 10³ Carrier 2 Mn-Mg-Sr-BasedFerrite 63 0 68 9.96 × 10¹¹ 2.30 × 10⁹ 4.17 × 10² Carrier 3 Magnetite 680 82 4.80 × 10¹⁴ 3.50 × 10¹² 1.37 × 10² Carrier 4 Cu-Zn-Based Ferrite 600.5 64 2.00 × 10¹⁵ 9.70 × 10¹¹ 2.06 × 10³ Carrier 5 Mg-Based Ferrite 661.0 58  6.5 × 10¹⁴  3.1 × 10¹³  2.1 × 10² Comp. Magnetite 63 0 82  2.6 ×10¹⁸  4.0 × 10¹²  6.5 × 10⁵ Carrier 1 Comp. Mn-Based Ferrite 60 0 951.50 × 10¹⁵ 1.10 × 10¹⁴ 1.36 × 10¹ Carrier 2 Comp. Mg-Based Ferrite 543.4 58 4.40 × 10¹⁷ 5.00 × 10¹⁶  8.8 × 10⁰ Carrier 3 Comp. Mn-Mg-Sr-BasedFerrite 62 0 65 3.40 × 10¹⁴ 3.12 × 10⁹  1.09 × 10⁵ Carrier 4 Comp.Magnetite 62 0 82 3.40 × 10⁹  3.12 × 10⁸  1.09 × 10¹ Carrier 5

Examples 1 to 13 and Comparative Examples 1 to 10

[0069] Five parts by weight of a toner and 95 parts by weight of acarrier, as shown in Tables 4 and 5, were mixed with a turbuler shakermixer, to give each two-component developer.

[0070] The resulting two-component developer was loaded in a high-speedmachine of a modified apparatus of “SD2075” (commercially available fromSharp Corporation) in which the peripheral speed of the organicphotoconductor was adjusted to 600 mm/sec. Printing was carried out at aprinting ratio of 10% up to 50000 sheets and at a printing ratio of 2%for the 50000th sheet to the 100000th sheet. During the continuousprinting, the image densities after printing 1000 sheets (initialprinting) and after printing 100000 sheets, and the carrier sticking onphotoconductor, the background fogging and the toner scattering after100000 sheets were evaluated by the following methods. The results areshown in Tables 4 and 5.

[0071] [Image Density]

[0072] An optical reflective density is measured with a reflectivedensitometer “RD-915” (commercially available from Macbeth ProcessMeasurements Co.). The image density is evaluated by the followingevaluation criteria.

[0073] (Evaluation Criteria) ⊚: 1.4 or more ◯: 1.3 or more and less than1.4 Δ: 1.2 or more and less than 1.3 X: less than 1.2

[0074] [Carrier Sticking on Photoconductor]

[0075] The number of white spots caused by the carrier sticking onphotoconductor is counted when 10 sheets of solid images (10 cm×12 cm)are printed. The carrier sticking on a photoconductor is evaluated bythe following evaluation criteria.

[0076] (Evaluation Criteria) ⊚: 0 spots per sheet ◯: 1 spot per sheet Δ:2 to 5 spots per sheet X: 6 or more spots per sheet

[0077] [Background Fogging]

[0078] The degree of whiteness in a non-image-bearing portion ismeasured with a spectrophotometer “SZ-Σ90” (commercially available fromNihon Denshoku Kogyo K. K.), and the background fogging is evaluated bythe following evaluation criteria.

[0079] (Evaluation Criteria) ◯: less than 0.5 Δ: 0.5 or more and lessthan 1.0 X: 1.0 or more

[0080] [Toner Scattering]

[0081] The amount of toner scattering within the machine is determinedfor 6 seconds with a digital dust indicator “Model P-5H2” (commerciallyavailable from SHIBATA SCIENTIFIC TECHNOLOGY LTD.). The toner scatteringis evaluated by the following criteria.

[0082] (Evaluation Criteria) ⊚: 0 or more and less than 20 ◯: 20 or moreand less than 40 Δ: 40 or more and less than 60 X: 60 or more

[0083] TABLE 4 After 100000 Sheets Image Density Carrier After 1000After 100000 Sticking on Background Toner Toner Carrier Sheets SheetsPhotoconductor Fogging Scattering Example 1 Toner 1 Carrier 1 ⊚ ⊚ ⊚ ◯ ◯Example 2 Toner 1 Carrier 2 ⊚ ◯ ◯ ◯ ◯ Example 3 Toner 1 Carrier 3 ◯ ◯ ⊚◯ ◯ Example 4 Toner 1 Carrier 4 ◯ ◯ ◯ ◯ ⊚ Example 5 Toner 1 Carrier 5 ◯◯ ◯ ◯ ◯ Example 6 Toner 2 Carrier 1 ◯ ◯ ◯ ◯ ◯ Example 7 Toner 3 Carrier1 ◯ ◯ ◯ ◯ Δ Example 8 Toner 4 Carrier 1 ⊚ ⊚ ◯ ◯ ◯ Example 9 Toner 4Carrier 2 ⊚ ◯ ◯ ◯ ◯ Example 10 Toner 4 Carrier 4 ◯ ◯ ◯ ◯ ◯ Example 11Toner 5 Carrier 1 ⊚ Δ ◯ ◯ ⊚ Example 12 Toner 6 Carrier 1 ⊚ Δ ◯ ◯ ⊚Example 13 Toner 7 Carrier 1 Δ 502 ◯ ◯ ◯

[0084] TABLE 5 After 100000 Sheets Image Density Carrier After 1000After 100000 Sticking on Background Toner Toner Carrier Sheets SheetsPhotoconductor Fogging Scattering Comp. Toner 1 Comp. Δ X ◯ Δ ◯ Example1 Carrier 1 Comp. Toner 1 Comp. Δ X Δ ◯ Δ Example 2 Carrier 2 Comp.Toner 1 Comp. X X ◯ ◯ ◯ Example 3 Carrier 3 Comp. Toner 1 Comp. ◯ ◯ X XΔ Example 4 Carrier 4 Comp. Toner 1 Comp. ◯ ◯ X Δ Δ Example 5 Carrier 5Comp. Comp. Carrier 1 ◯ X ◯ ◯ Δ Example 6 Toner 1 Comp. Comp. Carrier 4◯ X ◯ ◯ ◯ Example 7 Toner 1 Comp. Comp. Carrier 4 ⊚ X ◯ Δ ◯ Example 8Toner 2 Comp. Comp. Carrier 4 ◯ X ◯ Δ ◯ Example 9 Toner 3 Comp. Comp.Carrier 4 Δ X ◯ Δ ◯ Example 10 Toner 4

[0085] It is seen from the above results that high-quality images can becontinuously obtained without causing the carrier sticking onphotoconductor in all of Examples 1 to 13. On the other hand, it is seenthat the carrier sticking on photoconductor, the toner scattering, and adecrease in the image density are caused in Comparative Examples 1 to 5in which the values of Rs/Rv of the carriers are not adjusted. Also, itis seen that the image density is drastically decreased in ComparativeExamples 6 to 10 in which a toner comprising only a hydrophobic silicaof a small particle size is used.

[0086] According to the present invention, there can be provided atwo-component developer which can continuously give high-quality images,even in a high-speed machine, without causing the embedment of silicaand the carrier sticking on photoconductor.

[0087] The present invention being thus described, it will be obviousthat the same may be varied in many ways. Such variations are not to beregarded as a departure from the spirit and scope of the invention, andall such modifications as would be obvious to one skilled in the art areintended to be included within the scope of the following claims.

What is claimed is:
 1. A two-component developer comprising: a toneronto which a hydrophobic silica having an average particle size of 25 nmor more is externally added, and a carrier having a saturationmagnetization of from 50 to 95 Am²/kg, wherein the carrier has a ratioof surface resistivity to volume resistivity of from 1×10² to 1×10⁴ m⁻¹at an electric field strength of 100 V/cm.
 2. The two-componentdeveloper according to claim 1, wherein the carrier has a surfaceresistivity of from 1×10¹⁰ to 1×10¹⁷ Ω.
 3. The two-component developeraccording to claim 1, wherein the toner has a volume-average particlesize of from 6 to 12 μm and the content of toner particles having aparticle size of 5 μm or less is 10 to 50% on a number basis of thetoner particles.
 4. The two-component developer according to claim 1,for use in an electrophotographic device comprising a photoconductorhaving a peripheral speed of 400 mm/sec or more.
 5. A method fordevelopment comprising applying the two-component developer of claim 1to an electrophotographic device comprising a photoconductor having aperipheral speed of 400 mm/sec or more, and developing a latent image.